ortho-Phenylene-Bridged Cyclic Oligopyrroles: Conformational Flexibilities and Optical Properties

ortho-Phenylene-bridged cyclic trimeric oligopyrrole C3 and hexameric oligopyrrole C6 were synthesized by Suzuki-Miyaura coupling reactions. The twisted structures of C3 and C6 were unambiguously revealed by X-ray diffraction analysis. The optical properties of these cyclic oligopyrroles were compared with linear oligopyrrole L3 and cyclic tetramer C4. The cyclic oligopyrroles exhibited large Stokes shifts and blue fluorescence with high quantum yields in solution and in the solid state. In addition, selective N-methylation and N-tolylation of C3 were used to tune the optical and electrochemical properties by changing the molecular twists and conformational flexibilities. Throughout these studies, the structure-property relationship of these cyclic strained oligopyrroles has been illustrated as an interesting molecular motif for novel cyclic π-conjugated systems.